Esters of di-(thiocarbamoyl)ethylene as juvenile hormone mimicking agents for control of insects

ABSTRACT

Compounds having the formula IN WHICH R is alkyl having 1 to 8 carbon atoms, R1 is hydrogen or alkyl having 1 to 4 carbon atoms, R2 is hydrogen or alkyl having 1 to 4 carbon atoms, R3 is alkyl having 1 to 8 carbon atoms, X is oxygen or sulfur and X1 is oxygen or sulfur.

United States Patent [1 1 Pallos Nov. 5, 1974 ESTERS OF DI-( THIOCARBAMOYUETHYLENE AS JUVENILE HORMONE MIMICKING AGENTS IHSEQTS [75] Inventor: Ferenc Marcus Pallos, Walnut Creek, Calif.

[73] Assignee: Stauffer Chemical Company, New

York, NY.

[22] Filed: May 26, 1972 [21] Appl. No.: 257,092

[52] US. Cl. 260/455 A, 260/482 B, 424/300 [51] Int. Cl. C07c 155/02 [58] Field of Search 260/455 A [56] References Cited UNITED STATES PATENTS 3,056,822 10/1962 D'Amico 260/455 A 3,344,163 9/1967 Frank et al. 260/455 A FOREIGN PATENTS OR APPLICATIONS 917,869 2/1963 Great Britain 260/455 A 918,892 2/1963 Great Britain 260/455 A 3/1948 Great Britain 260/455 A ll/l964 Germany 260/455 A OTHER PUBLICATIONS Primary ExaminerLowis Gotts Assistant ExaminerD. R. Phillips Attorney, Agent, or FirmEdwin H. Baker [57] ABSTRACT Compounds having the formula in which R is alkyl having 1 to 8 carbon atoms, R is hydrogen or alkyl having 1 to 4 carbon atoms, R is hydrogen or alkyl having 1 to 4 carbon atoms, R is alkyl having I to 8 carbon atoms, X is oxygen or sulfur and X is oxygen or sulfur.

10 Claims, No Drawings ESTERS OF DI-(THIOCARBAMOYL)ETHYLENE AS JUVENILE HORMONE MIMICKING AGENTS FOR CONTROL OF INSECTS metamorphosis of larvae to pupae and pupae to adults resulting in the formation of abnormal members of the treated species which may also be non-viable or sterile.

This ultimately leads, indirectly at least, to the destruction of a pest population.

The compounds of the present invention are believed to have the further advantages that they are non-toxic to warm blooded animals and are highly effective in controlling insects at low dosages.

One embodiment of the present invention is concerned with novel pesticidal compositions.

In another embodiment, the invention is concerned with the active pesticidal component of such compositions.

In still another embodiment, the invention is concerned with a process for controlling insects by hindering or impeding the metamorphosis and reproduction of the insects.

The compounds of the present invention that are useful in controlling insects are those having the formula in which R is alkyl having 1 to 8 carbon atoms, preferably 2 to 6 carbon atoms; R is hydrogen or alkyl having I to 4 carbon atoms, preferably hydrogen; R is hydrogen or, preferably, alkyl having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms; R is alkyl having 1 to 8 carbon atoms, preferably 2 to 6 carbon atoms; X is' oxygen or sulfur and X is oxygen or sulfur.

As indicated heretofore, the above compounds are useful in impeding the metamorphosis and/or the reproduction of-insects. The activity of the compounds is such that insects at any stage of their development can be effectively treated therewith.

The compounds of this invention can be prepared by the following reaction:

Preferably the reaction is carried out in a solvent such as water, with stirring by slowing adding the alkyl chloro(thio)formate or mixture of alkyl chloro(thio)- formates to the diamine in the presence of an acid acceptor, such as a solution of NaOH, at a temperature around 0C. followed by stirring at room temperature to complete the exothermic reaction. The reaction product is recovered by conventional techniques such as extracting with methylene chloride, washing the solvent phase with water, followed by drying with anhydrous MgSO Finally, the solvent is filtered and removed by vacuum stripping.

Preferably, the reaction is carried out using equal mole amounts of the reactants, although a slight excess of a reactant can be used.

In compounds where R and R are different and/or X and X are different then a mixture of desired compounds result which can be separated by conventional techniques.

Preparation of the compounds of this invention is illustrated by the following specific examples.

I Example I v N,N-diethyl-l ,2-bis(n-propylthiocarbamoyl) ethane C2115 C2H5 2.9 grams (0.025 mole), N,N-diethyl ethylene diamine, 25 milliliters water, 4.0 grams (50 percent) NaOH solution (0.05 mole) are mixed in a 3-neck flask equipped with a dropping funnel and a mechanical stirrer and stirring in an ice bath. 6.9 grams (0.05 mole) n-propylchlorothiolformate are slowly dropped into the mixture causing a exothermic reaction. The ice bath is removed and the reaction mixture is stirred at room temperature for A hour. The reaction product is recovered by extracting with 100 milliliters c1-nc1, and then washing it with milliliters water, followed by drying with MgSO The organic phase is filtered and stripped by yield 6.9 grams of the desired product. N P-1.5022. LR. and n.m.r. analysis confirm the structure.

The following is a table of certain selected compounds that are preparable according to the procedures described hereto. Compound numbers are as- "signed to each compound and are used throughout the remainder of the specification.

. Table l-Continued Compound Number R X R' R X R N 1 l i-C H S C H H S i-C H 47-52C. l2 n-C H, S i-C l-l, S n-C l-l 1.5145 13 i-C H, S i-C H, H S i C H 65-68C. l4 i-C H, S i-C H H S i-C,H,, 4246C. l5 i-C,H,, S H C H S i-C,H,, 1.5100 16 sec-C,H, S H C H S sec-C,H 1.5050 17 i-C,H, O C H H O i-C H 1.4482 I8 n-C,H S CH C H S n-C H; 1.5120 19 i-C H, S C H CH S i-C H 1.5085 20 i-C,H, S CH, C H, S i-C,H,, 1.5065 21 n-C,H S H CH, S n-C H 7 1.5200 22 i'C H, S CH, H S iC H, 23 i-C,H, 3 CH H S i-C ,H,, 38-40C. 24 i-C,H,, S H H S i-C,H,, 94-96C. 25 Z-methylbutyl S H C H S 2'methylbutyl Prepared in Example I.

The degree of activity of a candidate compound to hinder or impede the metamorphosis of insects is measured by treating the penultimate larval stage of a representative insect with the compound and examining it after its last molt toward the adult form for retention of immature features.

Specifically, yellow mealworm, Tenebrio molitor, L., larvae are maintained at 28C. and 40 percent humidity on a diet of bran flakes. Prepupae are collected from the culture and kept in separate containers. The pupae collected once daily, are l-25 hours old at the time of treatment. By means of a syringe, suitable amounts of candidate compounds in 0.5 or 1.0 ul of acetone are applied to the venter of Tenebrio molitor, L. pupae; Treated pupae are maintained at 28C. and 40 percent humidity until the adults emerged (usually within 6-8 days). Emerged adults are graded as positive, negative, or dead. To be considered a positive response, the presence of typical pupal cuticle, urogomphi, gin trap, and abnormal wings, etc., are required. For each test, 1 group of pupae was used.

The dose of a candidate compound per pupa that is needed to give a positive response in the above insecticidal evaluation test for 5 of the 10 pupae is determined. Table 11 shows these doses under the column ED the ED" being an abbreviation for effective dose.

TABLE II Compound Number ED rig/pupa 8 0.1 9 0.5 10 10. 11 0.1 12 0.5 13 2. 14- 3. 15 0.003 16 0.02 17 2. l8 l0. l9 10. 20 0.2 21 0.5 22 3.0 23 0.05 24 10.

The compounds of this invention are generally embodied-into a form suitable for convenient application. For example, the compounds can be embodied into pesticidal composition which are provided in the form of emulsions, suspensions, solutions, dusts, and aerosol sprays. In general, such compositions will contain, in addition to the active compound, the adjuvants which are found normally in pesticide preparations. In these compositions, the active compounds of this invention can be employed as the sole pesticide component or they can be used in admixture with other compounds having similar utility. The pesticide compositions of this invention can contain, as adjuvants, organic solvents, such as sesame oil, xylene range solvents, heavy petroleum, etc., water; emulsifying agents; surface active agents; talc; pyrophyllite; diatomite; gypsum; clays; propellants, such as dichlorodifluoromethane, etc. If desired, however, the active compounds can be applied directly to feedstuffs, seeds, etc., upon which thepests feed. When applied in such a manner, it will be advantageous to use a compound which is not volatile.

Thecompounds can also be combined with baits in a conventional manner.

The precise manner in which the pesticide compositions of this invention are used in any particular instance will be readily apparent to a person skilled in the art. Generally, the active pesticide compound will be embodied in the form of a liquid composition, for example, an emulsion, suspension, or aerosol spray. While the concentration of the active pesticide in the present compositions can vary within rather wide limits, ordinarily the pesticide compound will comprise not more than about 50 percent by weight of the composition. Preferably, however, the pesticide compositions of this invention will be in the form of solutions or suspensions containing about 0.1 to 1.0 percent by weight of the active pesticide compound.

What is claimed is:

1. A compound of the formula:

in which R is alkyl having 2 to 6 carbon atoms; R is hydrogen or alkyl having 1 to 4 carbon atoms; R is alkyl having 1 to 4 carbon atoms; R is alkyl having 2 to 6 carbon atoms; X is sulfur and X is sulfur.

2. The compound of claim 1 in which R is alkyl having 2 to 6 carbon atoms, R is hydrogen, R is alkyl having 1 to 3 carbon atoms, R is alkyl having 2 to 6 carbon atoms, X is sulfur and X is sulfur.

3. The compound of claim 1 in which R is alkyl having 2 to 6 carbon atoms, R is alkyl having 1 to 3 carbon atoms, R is alkyl having 1 to 3 carbon atoms, R is alkyl having 2 to 6 carbon atoms, X is sulfur and X is sulfur.

4. The compound of claim 1 in which R is isobutyl, R is hydrogen, R is ethyl, R is isobutyl, X is sulfur and X is sulfur.

5. The compound of claim 1 in which R is secondary butyl, R is hydrogen, R is ethyl, R is secondary butyl, X is sulfur and X is sulfur.

6. The compound of claim 1 in which R is n-propyl, R is hydrogen, R is ethyl, R is n-propyl, X is sulfur and X is sulfur.

7. The compound of claim 1 in which R is isopropyl, R is ethyl, R is hydrogen, R is isopropyl, X is sulfur and X is sulfur.

8. The compound of claim 1 in which R is isobutyl, R is ethyl, R is ethyl, R is isobutyl, X is sulfur and X is sulfur.

9. The compound of claim 1 in which R is isobutyl, R is methyl, R is ethyl, R is isobutyl, X is sulfur and X is sulfur.

10. The compound of claim 1 in which R is 2- methylbutyl, R is hydrogen, R is ethyl, R is 2- methylbutyl, X is sulfur and X is sulfur.

UNITED STATES PATENT OFFICE CERTIFICATE OF CQRRECTION Patent No. 3,8+6,4*-66 Dated November 5 1974 Invent fl Ferenc M. Pallos It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

IN THE CLAIMS:

In Claim 1 the formula that reads 0 R R o II I l 1 '2 R-XC-NCH N-C-X -R should read O R R l l I l 3 R-K-C-NCH CH N-C-X -R Signed and sealed this 151:1: day of .Epri l 1375. 

1. A COMPOUND OF THE FORMULA:
 2. The compound of claim 1 in which R is alkyl having 2 to 6 carbon atoms, R1 is hydrogen, R2 is alkyl having 1 to 3 carbon atoms, R3 is alkyl having 2 to 6 carbon atoms, X is sulfur and X1 is sulfur.
 3. The compound of claim 1 in which R is alkyl having 2 to 6 carbon atoms, R1 is alkyl having 1 to 3 carbon atoms, R2 is alkyl having 1 to 3 carbon atoms, R3 is alkyl having 2 to 6 carbon atoms, X is sulfur and X1 is sulfur.
 4. The compound of claim 1 in which R is isobutyl, R1 is hydrogen, R2 is ethyl, R3 is isobutyl, X is sulfur and X1 is sulfur.
 5. The compound of claim 1 in which R is secondary butyl, R1 is hydrogen, R2 is ethyl, R3 is secondary butyl, X is sulfur and X1 is sulfur.
 6. The compound of claim 1 in which R is n-propyl, R1 is hydrogen, R2 is ethyl, R3 is n-propyl, X is sulfur and X1 is sulfur.
 7. The compound of claim 1 in which R is isopropyl, R1 is ethyl, R2 is hydrogen, R3 is isopropyl, X is sulfur and X1 is sulfur.
 8. The compound of claim 1 in which R is isobutyl, R1 is ethyl, R2 is ethyl, R3 is isobutyl, X is sulfur and X1 is sulfur.
 9. The compound of claim 1 in which R is isobutyl, R1 is methyl, R2 is ethyl, R3 is isobutyl, X is sulfur and X1 is sulfur.
 10. The compound of claim 1 in which R is 2-methylbutyl, R1 is hydrogen, R2 is ethyl, R3 is 2-methylbutyl, X is sulfur and X1 is sulfur. 